Corrosion Science 123 (2017) 217–227

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Influence of chromium on the flow-accelerated corrosion behavior of low MARK

alloy steels in 3.5% NaCl solution
⁎
Shan Jiang , Feng Chai, Hang Su, Caifu Yang
Department of Structural Steels, Central Iron and Steel Research Institute, Beijing 100081, China

A R T I C L E I N F O A B S T R A C T

Keywords: The corrosion behavior of carbon steel and Cr-containing steels was investigated during flow-accelerated
Amorphization corrosion. The corresponding weight loss and electrochemical properties were determined by using a flow-loop
Chromium apparatus and a rotating-cylinder apparatus, respectively. The corrosion rate of the Cr-containing steels is lower
Flow accelerated corrosion than that of the carbon steel. Furthermore, the high corrosion resistance of these steels was closely correlated
Low alloy steel
with the properties of the rust layer formed on the steel surface. Cr leads mainly to inhibition of the cathodic
reaction. Therefore, Cr is suitable for improving the corrosion resistance of low alloy steel to flow-accelerated
corrosion.

1. Introduction of X65 steel in both oil-free and oil-containing solutions. Electrode

Flow-accelerated corrosion of metals has been studied for many
years. To enable application of laboratory test data to field operations,
flow-accelerated corrosion must be expressed in terms of geometry-
independent fluid flow parameters that are common to all hydrody-
namic systems. The mass transfer coefficient is the main parameter used
to describe flow-accelerated corrosion. Therefore, different apparatuses
are associated with distinct mass transfer conditions, such as flow loop
[1–6], rotating cylinder [7–9], and jet impingement[10–13]. Never-
theless, for the same laboratory test environment or field operations,
the flow velocity is the only primary parameter that affects the oxygen
diffusion rate.
Most studies of flow-accelerated corrosion of metals have focused
on the corrosion behavior of Cu alloys [14,15], stainless steels [16–20],
and carbon steel [21–23]. The corrosion rate of metals in a fluid
environment is significantly higher than that in a stagnant environ-
ment. Previous studies [24] have proposed that the corrosion rate
should increase with increasing flow velocity due to an increase in
oxygen diffusion and break-down of the protective films on the metal
surface. However, Li et al. [25] argue that the shear stress generated by
multi-phase flow is unable to break down the protective rust layer.
Chen et al. [26] validated that excellent oxygen diffusion in the bulk
solution was attributed to a high flow velocity. This occurs only in cases
where mass transfer is the rate-determining step of the reaction. Zhang
et al. and Tian et al. [27,28] investigated the corrosion behavior of X65
pipeline steel in the simulated oil/water emulsion, and proposed that
mass-transfer of oxygen plays an important role in the cathodic reaction
rotation accelerates the oxygen diffusion and the cathodic reduction.
Moreover, the elevating of solubility of oxygen in oil containing
solution results in an increasing of limiting diffusive current density.
Previous studies[29,30] found that, after long-term exposure, the
surface rust formed on weathering steel (which contains a small amount
of Cu, Cr, and P) consists of two layers. The addition of Cr to low alloy
steels can significantly reduce the corrosion rate during atmospheric
exposure. The protective rust layer formed on the surface of weathering
steels is composed of an X-ray amorphous substance or a goethite-type
phase. This layer is described as α-(Fe1-x,Crx)OOH, which forms owing
to the concentration of Cr in the inner rust layer. The inner layer of the
nano-sized FeOOH contains a considerable amount of Cr[31]. This Cr-
substituted FeOOH acts as both the final stable protective layer and the
superior protective layer. Previous work demonstrated that the con-
centration of Cr in the Cr-goethite results in dense aggregation of small
crystals that yield the high protective ability of the rust layer for
protection against atmospheric corrosion[29,32]. While many studies
[33–36] indicated that a pseudopassivation film formed on some Cr-
containing steels leads to low corrosion rate in CO2 corrosion environ-
ment, and this pseudopassivation film mainly consisted of Cr(OH)3.
Few systematic studies have been reported on the corrosion
resistance of low alloy steels in flowing NaCl solutions; reports
describing the effect of Cr on the characteristics of the rust layer
formed on low alloy steels during corrosion in fluid environments are
especially rare. Therefore, this study focused on the corrosion behavior
of carbon steel and Cr-containing steels during immersion in aqueous
NaCl solution. The goal of this work was to gain a better understanding

⁎
Corresponding author.
E-mail address: jiangshan2200@sina.com (S. Jiang).

http://dx.doi.org/10.1016/j.corsci.2017.04.024
Received 20 September 2016; Received in revised form 19 April 2017; Accepted 22 April 2017
Available online 08 May 2017
0010-938X/ © 2017 Elsevier Ltd. All rights reserved.
S. Jiang et al.
Fig. 1. Schematic of flow loop apparatus.
of the influence of Cr addition on the flow-accelerated corrosion of low
alloy steels.
2. Experimental method
2.1. Flow loop
A schematic of the flow loop is shown in Fig. 1. The flow loop was
constructed with 3.5 cm of I.D.-schedule PVC pipe. The loop contained
a 40 L polyethylene reservoir, variable frequency centrifugal pump for
flow-velocity control, flow meter, and refrigerator for temperature
control. Flow velocities ranging from 0 to 2.4 m/s could be obtained.
The test section of the flow-loop apparatus consists of four 900-mm
(height) test pipes, and each pipe contains eight plate-like specimens
simultaneously. In the present study, only one (pipe No.2) of the four
test pipes was used for the flow accelerated corrosion experiment.
Specimens used for direct-weight loss measurements and rust-layer
analysis for flow-loop test were inseted in the specimen holder, which is
made from PVC, and then the specimens holder was fixed in the test
pipe by fixtures. Of the eight specimens, counted from up-stream to
down-stream, the fourth and eighth specimens were used for rust-layer
analysis, and the others for direct weight-loss measurements. In each
test, the eight specimens had the same chemical composition, in order
to prevent the influence of the variation of Cr content on the corrosion
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Corrosion Science 123 (2017) 217–227
behavior of carbon steel and Cr-containing steels.
2.2. Rotating cylinder
The through-thickness direction of the experimental steel plate, the
chemical composition and microstructure were different between the
central and surface positions of the steel plate because of composition
segregation. In addition, the exposure area of experimental steels was
the surface of the steel plate. Furthermore, the test surface must be an
arcuate one. If the specimen is machined to a cylindrical shape directly,
the chemical composition and the microstructure on the arcuate surface
would be nonuniform. Thus, the diameter of the rotating cylinder
should be large enough to avoid this nonuiform test surface of speci-
men. Therefore, the diameter of the polytetrafluoroethylene cylinder
was designed to be 130 mm, and the length of the cylinder is 45 mm.
The distance between upper surface of the cylinder and liquid level was
200 mm. The diameter of reactor where the rotating cylinder was
immersed was 400 mm, and the length of reactor was 500 mm. The
distance between the lower surface of the cylinder and the bottom of
the reactor was also 200 mm. Fig. 2 shows the design of the rotating-
cylinder system. It should be pointed out that the cylinder used in the
present study is not a typical rotating cylinder, which is a cylindrical
working electrode. The working electrodes used in the present study are
separated and embedded in the insulating rotating cylinder.
S. Jiang et al. Corrosion Science 123 (2017) 217–227

Fig. 2. Schematic of rotating cylinder apparatus.

Table 1
Chemical composition of experimental steels, wt%.

C Mn Si P S Cr

Carbon steel 0.082 0.63 0.24 0.012 0.0036 –

Fe-0.5Cr steel 0.075 0.61 0.24 0.011 0.0030 0.46
Fe-2Cr steel 0.078 0.60 0.21 0.018 0.0020 1.98
Fe-5Cr steel 0.082 0.60 0.15 0.0012 0.0040 4.94

Fig. 4. The weight loss of experimental steels exposed for 384 h in stagnant and flowing
conditions with various velocities.

2.3. Test solution

The experiments were performed in a NaCl solution (pH: 6.8) at a

Fig. 3. Dimension of specimens used for flow loop apparatus and rotating cylinder
apparatus.
Rotation speeds of 100, 200, and 300 rpm were considered. For the
stationary reference electrode, the distance between reference and
working electrodes change with the cylinder rotating. This may lead
to the change of the ohmic drop. However, cylinder rotation increases
the corrosion potential of the experimental steels, and also decrease the
change of the ohmic drop. Furthermore, all specimens were tested
under essentially identical conditions. These specimens were electri-
cally insulated from each other and all three specimens were used for
potentiodynamic polarization studies. When testing potentiodynamic
polarization curves, one of the three specimens was connected with the
copper shaft by wire. After testing, the wire was cut off, and the copper
shaft was connected with the next specimen by a wire.
temperature of 25 °C, the concentration of NaCl is approximately to
0.62 mol/L(mass percent: 3.5 wt%). Owing to recirculation, the solu-
tion temperature increased from 23 °C to ∼26 °C during the initial
stage of testing with the flow-loop apparatus. In the case of the rotating-
cylinder apparatus, the solution temperature was controlled by a water-
bath.
2.4. Specimens
Specimens of Cr-containing steels and carbon steel were exposed to
a fluid corrosion environment for 384 h. The chemical composition of
each steel is listed in Table 1. The severity of corrosion, exhibited by the
steels, was evaluated via the weight loss.
Prior to exposure, specimens used in the flow-loop and rotating-
cylinder tests were all rinsed with acetone and then air-dried; exposure

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S. Jiang et al. Corrosion Science 123 (2017) 217–227

Fig. 5. Potentiodynamic polarization curves of experimental steels exposed for 0 h and 384 h in stagnant and flowing conditions with various velocities. (a) corroded for 0 h at stagnant
condition; (b) corroded for 0 h with rotating speed at 100 rpm; (c) corroded for 0 h with rotating speed at 200 rpm; (d) corroded for 0 h with rotating speed at 300 rpm; (e) corroded for
384 h at stagnant condition; (f) corroded for 384 h with rotating speed at 100 rpm; (g) corroded for 384 h with rotating speed at 200 rpm; (h) corroded for 384 h with rotating speed at
300 rpm.

areas of 8 cm2 and 3.01 cm2, respectively, were realized for these
specimens. All specimens were tested under essentially identical
conditions. Fig. 3 shows the specimens (including the dimensions) used
in this work.
2.5. Direct weight-loss measurements
Prior to exposure, the specimens for weight loss measurements were
rinsed with acetone, air-dried, and weighed with a microbalance. After
each exposure, the specimens were descaled, via immersion in solution
of 500 mL HCl + 3.5 g hexamethylenetetramine, and then successively
rinsed in distilled water and acetone. The specimens were then air-dried
and re-weighed in order to calculate the weight loss resulting from
corrosion.
2.6. Electrochemical measurements
Potentiodynamic polarization curves were obtained at a voltage
scan rate of 30 mV/min using a Princeton Applied Research Model 173
potentiostat and a Model 175 Universal programmer.
2.7. Rust-layer analysis
The specimens covered by a rust layer were fixed by an epoxy resin.
The cross-section of the fixed specimens were mechanically ground by
silicon carbide papers (grades 150–1000) and then polished with a
diamond paste. Subsequently, the cross-section of the surface corrosion
products was characterized via scanning electron microscopy, electron
probe micro-analysis, and Raman spectroscopy. The distribution of
several important elements in the rust layers was determined by using a
Shimadzu Model EPM810 electron probe micro-analyzer (accelerating
voltage: 15 kV, sample current: 0.1 μA). Raman spectrum was obtained
with a LabRAM HR800 Raman Spectrometer system. The laser power
measured on the sample was 2 mW and a spot diameter of 1–2 μm. The
wavelength of excitation source is 532 nm.
The sample consisting of an inner rust layer was subjected to 1 h of
ultra-sonic vibration in an ethanol solution in order to separate the
products formed in the layer. The resulting solution was then dripped
on a carbon film. After the ethanol evaporated, observation and phase
analysis of the film were performed on a FEI FECNAI G2 F20
microscope. In addition, the valence state of Cr was determined and
phases formed on the inner rust layer were identified via X-ray
photoelectron spectroscopy (energy resolution: 0.5 eV, anodic target:

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S. Jiang et al.
Fig. 6. Potentiodynamic polarization curves of experimental steels exposed for various periods with rotating speed at 100 rpm. (a) Carbon steel; (b) Fe-2Cr steel; (c) Fe-5Cr steel.
Al, high vacuum: 6.7 × 10−8 Pa).
3. Results
3.1. Weight loss of experimental steels corroded for 384 h
Fig. 4 shows the material degradation, in the form of weight loss, of
all the steels tested by the pipe line apparatus. After 384 h of corrosion
in stagnant and flowing conditions with various flow velocities. There
was no significant difference in weight loss between the carbon steel
and Cr-containing steels in stagnant condition. With the solution flow,
the carbon steel exhibited the highest weight loss. The weight loss of
the Cr-containing steels was accordingly less than that of the carbon
steel, and decreased with increasing Cr content of the steel. Moreover,
the weight loss of both steels increased linearly with increasing flow
velocity.
3.2. Polarization curve measurements in stagnant and flowing conditions
with various electrode rotating speeds
Fig. 5 shows the potentiodynamic polarization curves of experi-
mental steels immersed in 3.5 wt% NaCl solution at 25 °C in stagnant
and flowing conditions with various electrode rotation speeds. A
limiting current density occurs in stagnant condition. In flowing
conditions with various flow velocities, the cathodic current density
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Corrosion Science 123 (2017) 217–227
of the experimental steels increases and the slope of cathodic curves
decrease with increasing rotation speed. Moreover, the cathodic
polarization curves of the steels were almost identical at high cathodic
overpotentials.
The current density associated with anodic shift of these steels
decreased, at various rotation speeds and stagnant conditions, with
increasing Cr content of the steels. Furthermore, the rate of cathodic
reaction was lower than that of the anodic reaction.
After corrosion progressed for a certain time, the diffusion of the
depolarizer and the dissolution of Fe were affected by the rust layer
formed on the steel surface. The cathodic and anodic reactions occurred
at quite similar rates and, hence, presenting a hybrid control character-
istic. In this case, the potential and the current density of the
potentiodynamic polarization curves decreased, thereby the corrosion
current density also decreased significantly. The difference in the
anodic current density of the experimental steels decreased with
increasing flow velocity, while the difference in the cathodic current
density of the steels increased significantly with increasing flow
velocity.
Fig. 6 shows the polarization curves of carbon steel, Fe-2Cr steel,
and Fe-5Cr steel at rotation speed of 100 rpm for different immersion
times. For both of carbon steel and Cr-containing steels, the effect of
corrosion period is focused on the cathodic polarization curves, and
there was no obvious influence on the anodic polarization curves. For
carbon steel, a limiting current occured at a rotation speed of 100 rpm
S. Jiang et al.
Fig. 7. Corrosion potential of experimental steels tested in flow loop apparatus in stagnant and flowing conditions with various velocities. (a) tested at stagnant condition; (b) tested in
flow velocity at 0.4 m/s; (c) tested in flow velocity at 0.8 m/s; (d) tested in flow velocity at 1.6 m/s.
when it corroded for 48 and 96 h. The cathodic current density
gradually decreased until carbon steel was corroded for 192 h, and
then the current density of cathodic polarization curves increased when
it was corroded for 384 h. The slope of cathodic shift also decreased
with the corrosion period. For Cr-containing steels, a limiting current
was also observed when it was corroded for 48 h and 96 h. The
tendency of variation for cathodic current is similar to that of carbon
steel, but the extent of variation is lower than that of carbon steel. The
rust layer formed on experimental steels played an important role on
the cathodic reaction.
Fig. 7 shows the time dependence of the corrosion potential in
stagnant and flowing conditions at various velocities, as determined by
the flow loop apparatus. During the first 24 h of corrosion, the
corrosion potential decreased sharply and stabilized thereafter. The
corrosion potential of both the carbon steel and Cr-containing steels
increased with solution flow and with increasing flow velocity of the
solution. In addition, the potential increased with increasing Cr content
of the steels and was higher than that of the carbon steel. However, the
difference in the potential of these steels decreased with increasing flow
velocity, especially for carbon steel, Fe-0.5Cr, and Fe-2Cr steels tested
at a velocity of 1.6 m/s.
3.3. Distribution of Cr in the rust layer of the Cr-containing steel
Fig. 8 shows the distribution of Cr in the rust layer formed on the Cr-
containing steel tested at a flow velocity of 1.6 m/s. As in a previous
study[32], these results suggest that Cr is mainly distributed in the
metal/rust interface, i.e., the inner rust layer is enriched with Cr. The
main difference of the rust constituents between carbon steel and Cr-
containing steels was that the inner rust layer formed on the Cr-
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containing steels contained a certain amount of Cr. Therefore, the
difference of the corrosion behavior between carbon steel and Cr-
containing steels is attributed to the difference on the inner rust layer
formed on the steels. In light of this interface enrichment, the effect of
Cr on the formation of the inner rust layer was investigated in further
detail.
3.4. Structure of the inner rust layer of the experimental steels
Fig. 9 shows the Raman spectroscopy results of the corrosion
products formed on the carbon steel and Cr-containing steels tested at
a flow velocity of 1.6 m/s; these products are located in the metal/rust
interfaces of each steel. The peak parameters corresponding to each
component are presented in Table 2. In addition, the products are
characterized by a broad band at 500–800 cm−1 for Cr-containing
steels and the spectra intensity decrease. This suggests that increasing
Cr content leads to amorphization of the products, which may consist of
FeCr2O4, FeOOH and Fe(OH)3, as indicated by the position of the
corresponding characteristic peaks. Furthermore, a new peak, with an
FWHM of 100 cm−1, occurs at 850 cm−1. Rahman[41] and Ren[42]
also reported that a new peak occurs at 826.4 and 850.2 cm−1,
respectively. In the present study, the peak near 850 cm−1 is attributed
to a chromium species, resulting from the reaction between Cr in
solution and iron oxide.
3.5. TEM analysis of corrosion products formed on the carbon steel and Cr-
containing steel
TEM images (Fig. 10) of the inner rust layers formed on the two
experimental steels reveal remarkable differences in both the morphol-
S. Jiang et al. Corrosion Science 123 (2017) 217–227

Fig. 8. The distribution of Cr in the rust layer formed on the Cr-containing steel.

Table 2
The peak parameters corresponding to each component analyzed by Raman spectroscopy,
cm−1.

Carbon steel Fe-0.5Cr Fe-2Cr steel Fe-5Cr Reference

steel steel

FeOOH/Fe 692 695 699 699 [37]

(OH)3
γ-FeOOH 262 278 – [38]
α-FeOOH 217,305,390 217, 385 217,387 [38,39]
FeCr2O4 – 592 595 595 [40]

steel, the corrosion products appeared flakes-like and gave rise to a

blurry diffraction pattern(diffusion ring), which is consistent with the
amorphization of these products. EDS analysis of different corrosion
products confirm the Cr enrichment of the product formed on the Cr-
containing steel.

3.6. State of Cr in the corrosion product

In the case of the Cr-containing steel, cross-sectional observation of

Fig. 9. Raman spectroscopy of corrosion products formed on the metal/rust interfaces of
experimental steels with flow velocity at 1.6 m/s.
ogy and crystallinity of the rust products. In the case of the plain carbon
steel, the products which gave rise to sharp diffraction patterns, were
formed in the inner rust layer. However, in the case of the Cr-containing
the rust (via EPMA)revealed that Cr was distributed over the metal/rust
interface. Fig. 11 shows the results from XPS analysis of the rust layer
and the resulting spectra were analyzed using the Casa-XPS software.
The Cr 2p3/2 high resolution spectra were fitted by using theoretical
multiplet peak. The peak parameters of each component are presented
in Table 3. The Cr 2P3/2 peak from the Cr-containing steel is associated
with at least three different phases namely, Cr(OH)3 [43], CrOOH[44],

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Fig. 10. TEM analysis of corrosion products formed on the Carbon steel and Cr-containing steel. (a) transmission electron micrograph of inner rust formed on carbon steel; (b)
transmission electron micrograph of inner rust formed on Cr-containing steel; (c) electron diffraction of corrosion products formed on carbon steel; (d) electron diffraction of corrosion
products formed on Cr-containing steel; (e) EDS analysis of corrosion products formed on carbon steel; (f) EDS analysis of corrosion products formed on Cr-containing steel.

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hand, the decrease of slope of cathodic shift means that diffusion of

depolarizer is sufficient. It is obvious that there is a contradiction
between suppression of O2 diffusion and sufficient diffusion of depolar-
izer. Therefore, there is another depolarizer that was introduced into
the cathodic reduction reaction.
The rust layer contains γ-FeOOH, which may act as another
oxidizer. The reduction of γ-FeOOH to the Fe2+-state intermediate,
i.e., {FeOHOH}, leads to continuous dissolution of the anode.
According to Stratmann[45], this type of reduced lepidocrocite main-
tains the same crystallographic structure as γ-FeOOH for Fe2+-doping
concentrations(in the lattice)of < 2%–4%, where irreversible formation
of Fe3O4 begins. This doping transforms the reduced lepidocrocite into
an electronic conductor with a crystallographic structure that allows
ionic conduction[46]. A significant amount of the available γ-FeOOH,
after reduction to the conducting reduced lepidocrocite, coats the
surface developed by the porosity of the rust layer. Furthermore, a
connection with the underlying metal allows the reduced lepidocrocite
on the surface of the pores to act as a cathodic area and oxygen can then
be reduced on that surface. Iron is oxidized on the small metal area in
Fig. 11. XPS analysis of corrosion products formed on the Cr-containing steel. contact with the electrolyte, at the bottom of the pores, whereas the
reduction reaction occurs on the large cathodic area formed by the
Table 3 reduced γ-FeOOH. This reduction reaction requires electrons, and starts
The peak parameters of each component analyzed by XPS, eV.
at the metal/rust interface. The reduction reaction occurs across the
Position Product FWHM Area% Reference entire reducible surface of γ-FeOOH. The reduced γ-FeOOH coats the
rust layer and, hence, this layer becomes a large cathodic area.
577.1 Cr(OH)3 2.6 43.93 [43] However, the amount of reduced lepidocrocite varies with the
577.2 CrOOH 2.6 34.92 [44] applied potential. During wet corrosion, the rust layer formed on the
575.9 FeCr2O4 1.2 8.48 [43]
steel is sufficiently reduced at potentials lower than
577.0 1.2 8.07 −200 mVSHE(−443.8 mVSCE). The electron transfer reaction can there-
577.9 1.2 3.15 fore occur inside the oxide scale containing Fe2+ highly doped electron-
578.9 1.2 1.45 conducting γ-FeOOH particles[46].
The results show that the corrosion rates of the Cr-containing steels
are lower than those of the carbon steel. And for Cr-containing steels,
and FeCr2O4[43]. This indicates that Cr was incorporated into the iron
the cathodic reaction was obviously suppressed by Cr addition. The
oxide as a trivalent ion, and Cr3+ participated in the formation process
suppression of cathodic reaction enhanced with increasing Cr content in
of the iron oxide.
the steel. In addition, Raman spectra analysis indicated that increases in
the Cr content of the steels was accompanied by amorphization of the
4. Discussion rust layer formed on the Cr-containing steels. This difference in the
corrosion behavior is attributed to Cr enrichment of the rust layer
In the present study, the working electrode was designed to be a (formed on the Cr-containing steels) in the presence of Cr-doped oxides;
cubic one with an arcuate exposed area. Therefore, the working TEM results concur with this assertion. The XPS results suggested that
electrodes embedded in the insulating rotating cylinder show the Cr was incorporated into the iron oxide as a trivalent ion. The
hydrodynamics characteristics of a rotating cylinder, but theirs electro- incorporation of Cr3+, in the solution, into γ-FeOOH may lead to a
chemical characteristic is more complex than the traditional cylindrical decrease in the electronic conductivity of the reduced γ-FeOOH, owing
electrodes. to the afore mentioned amorphization. Therefore, the rust is unable to
The distance between Luggin probe and an individual working act as a large cathode even at potentials lower than 200 mVSHE. This
electrode increases as the electrode is rotated away from the Luggin suggests that Cr inhibits oxygen reduction during the flow-accelerated
probe, and after reaching the position of 180° from the Luggin probe, corrosion process. As such, during the flow-accelerated corrosion
decreases again. Therefore, the ohmic drop may be affected by the process, Cr in the inner rust layer acts mainly as an inhibitor of the
change of the distance between Luggin probe and the electrode. cathodic reaction.
However, cylinder rotating increases the corrosion potential of experi- In a fluid environment, the flow velocity is the primary parameter
mental steels, thereby decreasing the change of the ohmic drop. that determines the corrosion rate of experimental steels. In this study,
Furthermore, all the specimens were tested in the same method, and the weight loss and electrochemical properties of experimental steels
the testing environments can be considered identical. Therefore, the were determined at various flow velocities by using a flow loop
experiment results can be compared with each other. apparatus and a rotating cylinder apparatus, respectively. The results
The potentiodynamic polarization curves suggest that diffusion of revealed that the weight loss of each steel increased with increasing
the depolarizer is the rate-determining step of the corrosion period, flow velocity, which resulted in an increased rate of oxygen diffusion.
where the steel surface is rust free. In this study, dissolved oxygen may However, the effect of the velocity on the anodic or cathodic reaction
act as an oxidizer. Nevertheless, oxygen cannot be reduced on the rust should be further discussed.
layer formed on the surface, as the rust is non-conducting. The potentiodynamic polarization curves show that the difference in
The current density and the slope of cathodic polarization curves of the cathodic current density of the steels increases significantly with
carbon steel decreased with the corrosion period until corroded for increasing flow velocity, but the difference in anodic current densities
192 h when corroded for 384 h, the slope of cathodic polarization decrease obviously, and the anodic current densities of experimental
curves of carbon steel further decreased and the current density steels were almost identical at high rotating speed. As previously
increased. This suggests that, on the one hand, the diffusion of mentioned, two reduction reactions, oxygen reduction and Fe3+
depolarizer O2 was suppressed by formation of rust layer; on the other reduction to Fe2+, can lead to dissolution of the anode. The formation

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S. Jiang et al.
of Fe2+ depends on the corrosion potential. Furthermore, the difference
in the corrosion potential of the carbon steel and Cr-containing steels
decreases with increasing flow velocity. This leads to only slight
differences in Fe2+ formation in the rust layers formed on the steels.
However, amorphous rust layers formed on the Cr-containing steels can
inhibit oxygen reduction during corrosion. Moreover, the number of
amorphous products in the rust layer increased with increasing Cr
content of the steels. This suggests that, with increasing flow velocity,
more significant suppression of oxygen reduction occurs in high-Cr steel
than in low-Cr steel. Therefore, compared to the suppression of Fe3+
reduction, the inhibition of oxygen reduction plays a more important
role in improving the corrosion resistance of low alloy steels to flow-
accelerated corrosion. However, the proportion of oxygen reduction
and Fe3+ reduction occurring on the rust during corrosion cannot be
quantified from the present results.
Cr addition on steel can affect the rate of anodic dissolution.
Increasing Cr content in the steel resulted in a reduction in relative
area of ferrite in the microstructure, and ferrite acted as anodic area in
the electrochemical reaction. Therefore, the rate of anodic dissolution
decreased with increasing Cr content in the steel when polarization
curves of the experimental steels were tested. Thus, the difference in
anodic current densities of experimental steels can be attributed to the
difference in the microstructure of the steels.
The difference in the anodic current density of the experimental
steels decreased with increasing flow velocity (see Fig. 5), owing to
accelerated oxygen diffusion towards the electrode surface. This
accelerated diffusion enhances the formation of corrosion products
[27,28]. The rust layer formed on the steels at high flow velocity maybe
sufficiently thick and dense to suppress anodic dissolution during
corrosion, yielding only a slight difference in the anodic current density
of the steels. In stagnant condition and at low flow velocity, less product
formed on the steel surface than that formed at high flow velocity.
Therefore, lower levels of suppression occur at stagnant and low flow
velocity condition and, hence, the difference in the anodic current
density of the steels is greater than that occurring at high flow velocity.
It is also indicated that increasing the Cr content of the inner rust layer
cannot further enhance the inner rust performance of suppression of the
anodic dissolution in the corrosion process. While the difference in
cathodic curves of experimental steels is attributed to the difference of
the inner rust layer with various Cr contents.
However, further investigation is needed to determine whether the
corrosion resulting from oxygen-free oxide reduction will be inhibited
by the addition of Cr. In addition, the proportion of oxygen reduction
and Fe3+ reduction occurring on rust formed during corrosion of the
carbon steel and Cr-containing steel must be determined. The mechan-
ism governing the formation of amorphous substances on Cr-containing
steels must also be investigated in further detail.
Fluid flow results mainly in accelerated cathodic reaction. As
previously mentioned, Cr concentration in the inner rust layer leads
to suppression of the cathodic reaction that occurs during the flow-
accelerated corrosion process. Therefore, the addition of Cr can
improve the flow-accelerated corrosion resistance of low alloy steels.
5. Conclusions
The corrosion behavior of carbon steel and Cr-containing steels was
investigated during flow-accelerated corrosion. The main findings may
be summarized as follows:
(1) At various flow velocities, the carbon steel experienced greater
weight loss than the Cr-containing steels. Increasing the flow
velocity may lead to high levels of oxygen diffusion, thereby
intensifying the weight loss of these steels.
(2) The flow velocity results mainly in an accelerated rate of cathodic
reaction, by increasing the rate of oxygen diffusion. The velocity
also affects the corrosion potential, and may influence the forma-
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Corrosion Science 123 (2017) 217–227
tion of Fe2+, which results in dissolution of the anode.
(3) The addition of Cr affects the corrosion behavior or formation
behavior of the corrosion product. In fact, the concentration of Cr in
the metal/rust interface leads to the formation of amorphous
products in the rust layer. This will lead to a decrease in the rate
of oxygen reduction during corrosion. Therefore, the main influ-
ence of Cr concentration in the inner rust layer on the corrosion
process is presumably the inhibition of the cathodic reaction.
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